KR20190089884A - Plasticizer composition - Google Patents

Abstract

R₁ 및 R₂는 동일하거나 상이하고, 직쇄형, 분지형 또는 고리형 하이드로카빌기를 나타낸다.The present invention relates to a plasticizer composition comprising a plasticizer (A) having a viscosity of at least 100 cP at 25 DEG C and an ester (B) having the formula (I)

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group.

Description

Plasticizer composition

The present invention relates to a plasticizer having a viscosity of at least 100 cP at 25 캜 and a plasticizer having a viscosity of not less than 100 cP at 25 캜 and a polymer such as a vinyl polymer, a halogen-containing polymer, chlorosulfonated polyethylene, cellulose ester, acrylic polymer, polyacetal, polystyrene, polyamide, ≪ / RTI > to the plasticizer composition.

Plasticizers are added to the materials to make them softer and more supple. The choice of plasticizer depends on various factors such as the performance specifications of the finished product, the price, the negative environmental impact, and the potential for adverse health effects to humans. For products designed for high temperature applications, plasticizers with low volatility, high compatibility and a low migration tendency, such as trimellitate esters or polymeric plasticizers, are preferred. For products designed where environmental and human health impacts are concerned, interest in high molecular weight bio-based plasticizers is increasing.

However, these plasticizers are not suitable for processing, such as pumping to a considerably difficult compounder, long mixing time requirements, low productivity, difficulty mixing between the polymer and other additives to induce the mixture, and defect points in the finished product. Which leads to the difficulty of the present invention.

To solve this problem, it is possible to preheat these high viscosity plasticizers, for example, prior to the dry mixing step, to reduce the time required to complete the dry mixing step, or to add benzylbutyl phthalate (BBP), dioctyl phthalate (DOP) There have been many attempts, such as a method of mixing with other low volatility phthalate plasticizers such as nephthalate (DINP) to reduce mixing time and decrease viscosity. However, this loses several key advantages of high viscosity plasticizers and makes finished products containing phthalates prohibited in some countries, particularly in Europe.

US20130210974A1 and US3354176A disclose PVC compositions using a plasticizer composition comprising a trimellitate plasticizer and a phthalate plasticizer.

US 8007918B2 discloses a plasticizer composition comprising trioctyl trimellitate and diundecyl phthalate for the cellulose ester.

US20060263556A1 discloses vinyl acetate-vinyl laurate copolymers using a plasticizer composition comprising trimellitate and an adipate plasticizer.

US6468258B1 discloses a plastic composition for medical containers comprising polyvinyl chloride, vitamin E, citrate ester, tri- (2-ethylhexyl) trimellitate (TEHTM or TOTM) and epoxidized oil.

Notwithstanding all the foregoing studies, it is possible to improve processability, plasticizer absorption rate and electrical volume resistivity, and also to improve the strength, thermal stability, weight stability at high temperatures, migration, We are still looking for an efficient plasticizer that can reduce the defects of the plasticized polymer.

Surprisingly, it has been found that this object can be achieved by a plasticizer composition comprising the following constituents:

a) a plasticizer (A) having a viscosity of at least 100 cP and

b) an ester (B) having the formula (I)

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group.

[summary]

A first embodiment of the invention relates to a plasticizer composition comprising a plasticizer (A) having a viscosity of at least 100 cP at 25 DEG C and an ester (B) having the formula (I)

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group.

Yet another embodiment of the present invention is a method of preparing a polymeric material comprising at least one polymer selected from the group consisting of vinyl polymers, halogen-containing polymers, chlorosulfonated polyethylene, cellulose esters, acrylic polymers, polyacetals, polystyrenes, polyamides, polyolefins, A polymer and a plasticizer composition comprising a plasticizer (A) having a viscosity of at least 100 cP at 25 DEG C and an ester (B) having the following formula (I):

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group.

A plasticizer composition comprising a plasticizer (A) having a viscosity of at least 100 cP at 25 캜 (not lower than 100 cP at 25 캜) and an ester (B) having the formula (I)

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group, preferably an alkyl group. R ₁ and R ₂ may have 1 to 15 carbon atoms. Preferably, R &_lt; 1 > is an alkyl group having from 1 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, and most preferably from 5 to 7 carbon atoms.

R ₂ is an alkyl group having 7 to 15 carbon atoms, more preferably 8 to 14 carbon atoms, and most preferably 8 to 10 carbon atoms.

Most preferably, the ester of formula (I) has from 11 to 23 carbon atoms. If the ester of formula (I) has less than 11 carbon atoms, it will be more volatile at room temperature. Conversely, if the ester of formula (I) has a number of carbon atoms above 23, it will be in solid form at room temperature, resulting in poor processibility and low miscibility with the polymeric resin.

The plasticizer (A) having a viscosity of not less than 100 cP, preferably in the range of 100 to 3,000 cP, is selected from the group consisting of trimellitate plasticizers, polymeric plasticizers, bio-based plasticizers a bio-based plasticizer, or a mixture thereof.

The trimellitate plasticizer is selected from the group consisting of tri-2-ethylhexyl trimellitate (TEHTM or TOTM), triisononyl trimellitate (TINTM), trimethyl trimellitate (TMTM), tri- (n-octyl, Is selected from trimellitate (ATM), tri- (heptyl, nonyl) trimellitate (LTM), n-octyltrimellitate (OTM) or mixtures thereof.

The polymerizable plasticizer may be selected from the group consisting of linear and / or branched polyesters, ethylene-vinyl acetate-carbon monoxide products, copolymers of butadiene and acrylonitrile, acrylic acid esters, ≪ / RTI > fumaric acid esters.

The polyester plasticizer may be selected from the group consisting of adipic, azelaic, fatty acids, mixed dibasic, phthalic, sebacic, succinic, It is the reaction product of glutaric acids and alcohol, glycol or polyhydric. Examples of such polyester plasticizers are adipic acid polyesters and adipic acid ether polyesters.

The bio-based plasticizer may be selected from the group consisting of isosorbide esters, sugar alcohols, acetylated fatty esters, acetylated oils, epoxidised fatty esters, Epoxidized oil, and isosorbide diester. The mixture of the plasticizer and the ester (B) of formula (I) may comprise an optional proportion of the plasticizer and the ester (B). Suitable mixtures comprise from 80% by weight to 99.7% by weight, preferably from 90% by weight to 99% by weight, more preferably from 92% by weight to 98.5% by weight, most preferably from 92% And may contain a plasticizer in an amount of 97% by weight. Likewise, suitable mixtures comprise from 0.3% to 20% by weight, preferably from 1% to 10% by weight, more preferably from 1.5% to 8% by weight, most preferably from 3% To 8% by weight of the ester (B). In one embodiment, the plasticizer composition comprises a mixture of the plasticizer and the ester (B) of any of the preceding embodiments, relative to the total content of the plasticizer composition.

Potential applications of the plasticizer compositions according to the present invention are as plasticizers for various polymeric resins. For example, the polymer resin may be selected from the group consisting of a vinyl polymer, a halogen-containing polymer, a chlorosulfonated polyethylene, a cellulose ester, an acrylic polymer, a poly But are not limited to, polyacetal, polystyrene, polyamide, polyolefins, or mixtures thereof, preferably acrylate elastomer, polyvinyl butyral, polyvinyl chloride polyvinyl chloride, epichlorohydrin, chlorosulfonated polyethylene, cellulose-acetate butyrate, and most preferably polyvinyl chloride.

The plasticizer compositions according to the present invention provide ease of processing that results in excellent compatibility with the polymers, especially polyvinyl chloride. This is due to the low viscosity of the plasticizer composition in which the ester of formula (I) acts as a viscosity reducing agent for high viscosity plasticizers and as an absorption rate increasing agent.

Another embodiment of the present invention relates to a polymer composition comprising at least one polymer and a plasticizer composition comprising a plasticizer (A) having a viscosity of at least 100 cP and an ester (B) of the formula (I).

The polymer of this embodiment is selected from the group consisting of vinyl polymers, halogen-containing polymers, chlorosulfonated polyethylene, cellulose esters, acrylic polymers, polyacetals, polystyrenes, polyamides, polyolefins or mixtures thereof, preferably acrylate elastomers, polyvinyl butyral , Polyvinyl chloride, epichlorohydrin, chlorosulfonated polyethylene, cellulose-acetate butyrate, and most preferably polyvinyl chloride.

In the polymer composition of this embodiment, the plasticizer composition comprising the plasticizer (A) and the ester (B) may be used in any embodiment as previously described herein.

The polymer composition according to the present invention preferably comprises the plasticizer composition in an amount of 1 to 120 parts by weight per 100 parts by weight of the polymer, more preferably 40 to 90 parts by weight per 100 parts by weight of the polymer.

Due to the fact that the plasticizer composition has a low viscosity and good compatibility with the polymer, and thus helps to lower the viscosity of the polymer when processing, mixing or forming the polymer composition, the polymer composition according to the present invention Easily processed, mixed or formed. Then still obtain a homogeneous distribution and the mixing time and cooling time can also be reduced, resulting in improved energy savings and higher productivity. In addition, this polymer composition has low defect points and high volume electrical resistance.

The polymer composition according to the present invention can be used as fillers, extenders, pigments, thermal stabilizers, UV stabilizers, viscosity regulators, rheological additives, At least one additive selected from the group consisting of a foam former, a foam stabilizer, an antistatic agent, an impact modifier, and lubricants.

The polymer composition according to the present invention may be used for the preparation of various types of polymers such as compounds, electric wire / cable compounds, wiring harnesses, sheets, tapes, Food packages, hoses, auto parts, seal liners, gaskets, medical supplies, construction materials, household items, Shoes, floor materials, synthetic leathers, tarpaulins, wallpapers, toys, and the like.

Hereinafter, the present invention will be further described by way of examples.

Method and Definition

1. Measurement of Viscosity of Plasticizer Composition

The viscosity of the plasticizer composition was carried out at 25 DEG C and the no. 0 Brookfield viscometer using a < RTI ID = 0.0 > 0 spindle. ≪ / RTI >

2. Measurement of plasticizer absorption time

The plasticizer absorption time is determined by the procedure of ASTM D2396-88. As the plasticizer absorption time, the time taken to add the plasticizer is measured until the kneading torque of the planetary mixer reaches a minimum.

3. Measurement of Physical Properties of Polymer Complex

a) Hardness

At 5 different points on the sample, a sample of 3 mm thickness was measured according to ASTM D2240 with a hardness meter or durometer (Type A), and the average value thereof was recorded.

b) The migration is the degree of plasticizer migration content.

A 1 mm thick sample is heated in an oven at 7O < 0 > C for 10 days, and the% migration is calculated by the following formula:

c) Volume resistivity (VR) is the degree of electrical volume resistance of the polymer composition.

The volume resistivity is measured according to ASTM D257. A 2 mm thick sample is placed between the two electrodes. For 60 seconds, the voltage is applied and the resistance is measured. The surface or volume resistivity is calculated and an apparent value is given (60 seconds electrification time).

d) Heat stability is the degree of durability of the polymer complex to heat.

Thermal stability is measured by a Metastat machine at 200 DEG C for 200 minutes. Visually inspect specimens 1 mm thick for discoloration and other signs of deterioration. The time (initial discoloration) at which the color of the sample starts to change and the time at which the sample starts to burn (burnt discoloration after burning) are recorded.

e) Weight stability (% weight loss) is the degree of decomposition of the polymer composition after heating.

A 1 mm thick sample was punched into a dumbbell shape and then heated at 100 占 폚 for 168 hours, and the% weight loss was calculated as follows.

f) The yellowness index is the degree of yellow discoloration of the sample.

A 1 mm thick sample is measured by a data color machine 600 (TM) according to ASTM D9125.

g) Tensile strength and elongation (% elongation)

The tensile strength and elongation are measured according to JIS K6723. The dumbbell shaped specimen is stretched at a crosshead speed of 200 mm / min using the test equipment U.T.M. The breaking point is measured. The tensile strength and elongation are calculated by the following formula.

h)% retention of tensile strength and elongation

Prior to measuring tensile strength and elongation according to JIS K6723, a dumbbell-shaped specimen of 1 mm thickness is heated in an oven at 80 or 100 占 폚 for 168 hours. The percent retention of tensile strength and elongation is calculated by the following formula.

i) Brittleness temperature is the temperature at which the polymer composition will withstand the low temperature before brittleness is found. The lower the brittle temperature, the higher the durability of the polymer composite at low temperature.

Using a Clash and Berg test (ASTM D746 brittleness test), a 2 mm thick sample is measured over a temperature range of -30 to -50 占 폚 at a temperature rate of 2 占 폚 / min.

j) Defect points are surface defects caused by unmelted material appearing on the surface of the sample. The number of defect points is counted.

Abbreviations used in the following table are as follows It has meaning. :

PVC: Polyvinyl chloride resin

TOTM: Tri (2-ethylhexyl) trimellitate (Tri (2-ethylhexyl) trimellitate)

DOTP: di (2-ethylhexyl) terephthalate (di (2-ethylhexyl) trimellitate)

DINP: di-isononyl phthalate

2EHB: 2-ethylhexyl butyrate

2EHH: 2-ethylhexyl hexanoate (2-ethylhexyl hexanoate)

DDP: dodecyl proprionate < RTI ID = 0.0 >

TDP: tetradecyl proprionate

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples (IE) and comparative examples (CE). However, the following examples are merely for the understanding of the present invention, and the present invention is not limited by the following examples.

1st Example

The mixture was stirred at ambient temperature for 5 minutes at 40 rpm to prepare the plasticizer composition and comparative plasticizer according to the present invention. Then, the physical properties were evaluated as shown in Table 1.

Example (% by weight based on total plasticizer composition weight) _{IE1 IE2 IE3 IE4 IE5 IE6 IE7 IE8 CE1 CE2 CE3 CE4 CE5 TOTM 96.2 98.0 96.2 95.0 93.0 96.2 96.2 - 100.0 96.2 96.2 96.2 - 2EHB 3.8 - - - - - - - - - - - - 2EHH - 2.0 3.8 5.0 7.0 - - 3.8 - - - - - DDP - - - - - 3.8 - - - - - - - TDP - - - - - - 3.8 - - - - - - DINP - - - - - - - - - 3.8 - - - DOTP - - - - - - - - - - 3.8 - - Adipic acid
polyester - - - - - - - 96.2 - - - 3.8 100.0 Viscosity*
(cP) 113 130 121 118 106 132 145 1664 172 155 161 170 2480 Plasticizer absorption time
 (second) 133 127 117 113 104 133 131 105 136 136 141 135 111}

* The viscosities of IE 1-7 and CE 1-5 were measured at rotational speeds of 2 rpm whereas the viscosities of IE 8 and CE 5 were measured at rotational speeds of 30 rpm.

As evident in Table 1, the presence of ester (B) (IE 1-7) of the formula (I) with TOTM results in lower viscosity and shorter plasticizer absorption rate than TOTM alone (CE 1). It has been found that the higher the content of ester (B) in formula (I), the lower the viscosity of the plasticizer composition and the faster the plasticizer absorption rate. In a second plasticizer of the same content, the plasticizer compositions (IE1, IE3, IE6 and IE7) comprising TOTM and the ester (B) of formula (I) comprise a plasticizer composition (CE2) comprising TOTM and DINP, TOTM and DOTP (CE3) comprising DOTP and polyester, and a plasticizer composition (CE4) comprising DOTP and polyester having a lower viscosity and a shorter absorption time. This will lead to easier processing of the plasticized polymer based on the plasticizer composition of the present invention as compared to the comparative plasticizer.

In addition, Table 1 shows that when the polyester plasticizer is mixed with the ester of formula (I) (IE8), the very high viscosity of the polyester plasticizer (CE5) is significantly reduced.

Lower viscosity and shorter plasticizer absorption times using plasticizer compositions comprising TOTM or polyester plasticizer and ester (B) of formula (I) lead to faster process times.

Second Example

According to the materials and contents as shown in Table 2 below, a polymer composition for high heat resistance cable application was prepared. The components were dry blended and then mixed with a mixing roll at 160 캜 for 4 minutes to prepare a polyvinyl chloride composition sheet for thermal stability test. For testing of other properties, the composition sheet was compressed to a predetermined size by compression molding at 180 DEG C for 5 minutes. The results are shown in Table 2.

According to Table 2, the polymer composition (polymer composition 1-6) comprising TOTM and ester (B) of formula (I) shows fewer defect points than the polymer composition (polymer composition 7) comprising TOTM alone . The higher the content of ester (B) in formula (I), the less defect points can be found and the tensile strength tends to increase. The addition of the ester (B) of the formula (I) in the plasticizer composition provides a higher volume electrical resistance than the addition of the other second plasticizer (polymer composition 8-10), while the tensile strength, thermal stability, Is maintained at a similar level. It has also been found that the polymer composition (polymer composition 10) comprising TOTM and polyester plasticizer has significantly lower volume electrical resistance and thermal stability than the polymer composition comprising ester (B) of TOTM and formula (I).

Polymer composition no. One 2 3 4 5 6 7 8 9 10 ingredient ( Weight portion )   PVC 100 100 100 100 100 100 100 100 100 100   Calcium carbonate 30 30 30 30 30 30 30 30 30 30   Calcium zinc stabilizer 4 4 4 4 4 4 4 4 4 4   IE1 50   IE2 50   IE3 50   IE4 50   IE5 50   IE6 50   CE1 50   CE2 50   CE3 50   CE4 50 Properties Hardness ¹ 89 88 89 89 89 89 89 89 89 88  Defect points (number) ** 20 20 14 11 9 11 25 17 17 18  Yellowing index * 10 10 10 10 10 10 10 10 10 10 Tensile strength (kg / cm ² ) ** 223 235 228 239 242 212 223 226 226 224  Elongation (%) ** 297 278 296 273 268 288 302 309 298 299  Implementation (%) * 0.5 0.6 0.5 0.6 0.6 0.7 0.5 0.6 0.5 0.5 Volume resistance
(× 10 ¹³ ohm.cm) ** 83 90 99 89 85 75 77 64 60 34  Thermal Stability **   - Initial color (min) 75 75 75 75 75 75 75 75 75 -   - Color after burning (min) 105 105 105 105 100 105 105 105 105 60  Thermal aging at 80 ° C **   - Retention of tensile strength (%) 100 93 99 93 94 100 97 97 100 100   - Retention of elongation (%) 94 100 95 100 100 95 93 91 100 97  Thermal aging at 100 ° C **   - Retention of tensile strength (%) 98 94 98 96 97 95 97 100 96 100   - Retention of elongation (%) 93 100 93 100 100 90 92 95 91 94  Weight loss (%) *   - @ 80 ℃ 0 0 0 0 0 0 0 0 0 0 - @ 100 ℃ 0 0 0 0 0 0 0 0.4 0 0  Brittle temperature (℃) * -20.6 -19.6 -18.5 -19.8 -20.0 -20.2 -18.3 -19.8 -20.4 -20.4

¹ Hardness is a control variable at a value of 88 +/- 2.

* The lower the value, the more favorable the resulting composition.

** The higher the value, the more favorable the resulting composition.

Claims (15)

a) a plasticizer (A) having a viscosity of at least 100 cP at 25 DEG C and
b) a plasticizer composition comprising an ester (B) having the formula (I)

R ₁ and R ₂ are the same or different and represent a linear, branched or cyclic hydrocarbyl group. The method according to claim 1,
Wherein R ₁ and R ₂ in the formula (I) are the same or different and represent a linear or branched alkyl group. The method according to claim 1 or 2,
Wherein R ₁ and R ₂ in formula (I) each independently have from 1 to 15 carbon atoms. In the preceding claim,
And R &_lt; 1 > is an alkyl group having 1 to 12 carbon atoms. In the preceding claim,
And R < ₂ > is an alkyl group having 7 to 15 carbon atoms. In the preceding claim,
Wherein the plasticizer (A) is selected from trimellitate plasticizers, polymerizable plasticizers, bio-based plasticizers or mixtures thereof. In the preceding claim,
Wherein the plasticizer (A) is present in an amount of from 80% by weight to 99.7% by weight, based on the total plasticizer composition. The method of claim 7,
Wherein the plasticizer (A) is present in an amount of 90 wt% to 99 wt% with respect to the total plasticizer composition. In the preceding claim,
Wherein the ester (B) is present in an amount of 0.3% to 20% by weight based on the total plasticizer composition. The method of claim 9,
Wherein the ester (B) is present in an amount of 1 wt% to 10 wt%, based on the total plasticizer composition. Polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, halogen-containing polymers, chlorosulfonated polyethylene, cellulose esters, acrylic polymers, polyacetals, polystyrenes, polyamides, polyolefins or mixtures thereof, preferably acrylate elastomers Use of a plasticizer composition according to the preceding claim for chlorohydrin, chlorosulfonated polyethylene, cellulose-acetate butyrate, most preferably polyvinyl chloride. At least one polymer selected from the group consisting of vinyl polymers, halogen-containing polymers, chlorosulfonated polyethylene, cellulose esters, acrylic polymers, polyacetals, polystyrenes, polyamides, polyolefins, 7. A polymer composition comprising a plasticizer composition according to any one of the preceding claims. The method of claim 12,
Wherein the polymer is polyvinyl chloride. 14. The method according to claim 12 or 13,
Wherein the plasticizer composition is present in an amount of 1 to 120 parts by weight per 100 parts by weight of the polymer, and preferably 40 to 90 parts by weight per 100 parts by weight of the polymer. 14. The method according to claim 12,
Wherein the polymer composition further comprises at least one additive selected from the group consisting of fillers, extenders, pigments, heat stabilizers, UV stabilizers, viscosity modifiers, flow additives, foam formers, foam stabilizers, antistatic agents, impact modifiers and lubricants.